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1.
Anion sensor properties of N‐alkyl‐substituted 1,4′‐diazaflavonium bromides in methanol–water were evaluated by UV–vis spectrometry. Pronounced changes were observed in the absorption spectra of all compounds for only OH?, CO32?, and CN? among F?, Cl?, Br?, I?, OH?, CO32?, NO3?, PO43?, CN?, SO42?, HSO4?, HCO3?, SCN?, NO2?, and P2O72? ions. Two new absorption bands at 385 and 685 nm accompanying the distinct color change for OH?, CO32?, and CN? ions were observed in case of all compounds. The color changes were from pink to blue for CO32? and OH? ions and from pink to purple for CN? ion. Thanks to the distinct color change, the compounds can be used as selective colorimetric anion sensors. Linear changes of absorbance of N‐heptyl‐substituted compound at 385 nm as a function of the ion concentration were used to determine CN? ion in water samples. Detection and quantification limits of the proposed method were 0.94 and 2.82 mg/L, respectively.  相似文献   

2.
《Analytical letters》2012,45(5):890-901
Abstract

A highly selective polyvinyl chloride (PVC) membrane electrode, based on N,N′‐(aminoethyl)ethylenediamide bis(2‐benzoideneimine) binuclear copper(II) complex [Cu(II)‐AEBB] as neutral carrier, was prepared for thiocyanate (SCN?) determination, which displays an anti‐Hofmeister selectivity sequence for a series of anions in the following order: SCN?>ClO4 ?>Sal? > I?>NO3 ?>Br?> Cl?>NO2 ?>SO3 2?>F?>H2PO4 ?>SO4 2?. The electrode exhibited near‐Nernst response for SCN? with a slope of –59.0 mV/decade over a wide concentration range (8.5×10?7~6.8×10?1 mol/L) with a detection limit of –5.0×10?7 mol/L in pH 5.0 phosphate buffer solution at 25°C. Alternating current (AC) impedance and equivalent circuits were used to investigate the thiocyanate response mechanism of the membrane doped with [Cu(II)‐AEBB].  相似文献   

3.
《Electroanalysis》2006,18(21):2070-2078
A highly selective potentiometric sensor for thiocyanate ion based on the use of a newly synthesized organo‐palladium ion exchanger complex dispersed in a plasticized poly(vinyl chloride) membrane is described. The sensor displays a Nernstian response (?57.8±0.2 mV decade?1) over a wide linear concentration range of thiocyanate (1.0×10?6–1.0×10?1 mol L?1 ), low detection limit (6.3×10?7 mol L?1), fast response (20 s), stable potential readings (±0.4 mV), good reproducibility (±0.9%), long term stability (8 weeks), high precision (±0.7%) and applicability over a wide pH range (4–10). Negligible interferences are caused by F?, Cl?, I?, Br?, NO3?, NO2?, CN?, SO42?, S2O32?, PO43?, citrate, acetate and oxalate ions. Under hydrodynamic mode of operation (FIA), the calibration slope is ?51.1±0.1 mV decade?1, the linear response range is 1.0×10?5–1.0×10?1 mol L?1 SCN? and the sample throughput is 40–45 per hour. The sensor is satisfactory used for manual and flow injection potentiometric determination of SCN? in the saliva and urine of cigarette smokers and non smokers. The data agree fairly well with results obtained by the standard spectrophotometric technique. Direct potentiometry and potentiometric titration of SCN? with Ag+ are also monitored with the sensor.  相似文献   

4.
A new chemodosimeter based on pyridinium‐fused pyridinone iodide ( PI ) has been obtained through a “clean reaction” method. This compound can detect CN? in aqueous solution with a high selectivity and rapid response. The detection of CN? occurs through the nucleophilic attack of CN? on the C?N bond, which induces the destruction of the π‐conjugation on the pyridinium ring. Support of this detection mechanism was obtained by 1H NMR titration, HR‐MS, and DFT calculations. Upon the addition of 10 equivalents CN? to a solution of PI in THF/H2O (1:1, v/v), a 57‐fold enhancement in fluorescence intensity was observed at the maximum emission wavelength of 457 nm. Meanwhile, the maximum absorption wavelength was also blue‐shifted from 447 nm to 355 nm. Other common anions such as BF4?, PF6?, F?, Cl?, Br?, I?, H2PO4?, ClO4?, CH3COO?, NO2?, N3?, and SCN? had little effect on the detection of CN?. The response time of PI for CN? was less than 5 seconds. The detection limit was calculated to be 5.4×10?8 M , which is lower than the maximum permission concentration in drinking water (1.9 μM ) set by the World Health Organization (WHO).  相似文献   

5.
We have designed and synthesized a new chemodosimeter, Benzolin-A, which selectively responds to toxic cyanide by dual colorimetric and fluorescence turn-on responses in buffered aqueous DMSO. In the presence of cyanide, we observe absorbance red shift of 108 nm (color changing from colorless to yellow) and fivefold fluorescence enhancement. The 1H NMR studies confirm the nucleophilic addition mechanism, and consistent with the experimental findings, the computational work predicts the feasibility of photoelectron transfer or energy transfer process in the native probe, as well as enhanced internal charge transfer in the Benzolin-A-cyanide adduct. Noteworthily, several background anions, such as F?, Cl?, AcO?, SCN?, HSO4 ?, NO3 ?, Br?, I? and H2PO4 ? exhibit none or insignificant optical perturbations.  相似文献   

6.
A highly selective chemosensor 1 based on an acylhydrazone group as binding site and naphthalene group as the fluorescence signal group were described, which could instantly detect CN? in water with specific selectivity and high sensitivity. The detection of cyanide was performed via the nucleophilic attack of cyanide anion on the carbonyl group, which could be confirmed by 1H NMR, 13C NMR, ESI‐MS and DFT calculations. The addition of CN? to sensor 1 induced a remarkable color change from colorless to yellow and generated a blue fluorescence, these sense procedure could not interfered by other coexistent competitive anions (F?, Cl?, Br?, I?, AcO?, H2PO4?, HSO4?, ClO4?, SCN?, S2?, NO3? and SO42?). The detection limits were 5.0×10?7 M and 2.0×10?9 M of CN? using the visual fluorescent color changes and fluorescence spectra changes respectively, which is far lower than the WHO guideline of 1.9×10?6 M . Test strips based on sensor 1 were fabricated, which could act as a convenient and efficient CN? test kit to detect CN? in pure water for “in‐the‐field” measurement.  相似文献   

7.
Lithium‐ion‐encapsulated [6,6]‐phenyl‐C61‐butyric acid methyl ester fullerene (Li+@PCBM) was utilized to construct supramolecules with sulfonated meso‐tetraphenylporphyrins (MTPPS4?; M=Zn, H2) in polar benzonitrile. The association constants were determined to be 1.8×105 M ?1 for ZnTPPS4?/Li+@PCBM and 6.2×104 M ?1 for H2TPPS4?/Li+@PCBM. From the electrochemical analyses, the energies of the charge‐separated (CS) states were estimated to be 0.69 eV for ZnTPPS4?/Li+@PCBM and 1.00 eV for H2TPPS4?/Li+@PCBM. Upon photoexcitation of the porphyrin moieties of MTPPS4?/Li+@PCBM, photoinduced electron transfer occurred to produce the CS states. The lifetimes of the CS states were 560 μs for ZnTPPS4?/Li+@PCBM and 450 μs for H2TPPS4?/Li+@PCBM. The spin states of the CS states were determined to be triplet by electron paramagnetic resonance spectroscopy measurements at 4 K. The reorganization energies (λ) and electronic coupling term (V) for back electron transfer (BET) were determined from the temperature dependence of kBET to be λ=0.36 eV and V=8.5×10?3 cm?1 for ZnTPPS4?/Li+@PCBM and λ=0.62 eV and V=7.9×10?3 cm?1 for H2TPPS4?/Li+@PCBM based on the Marcus theory of nonadiabatic electron transfer. Such small V values are the result of a small orbital interaction between the MTPPS4? and Li+@PCBM moieties. These small V values and spin‐forbidden charge recombination afford a long‐lived CS state.  相似文献   

8.
Poly(N‐isopropylacrylamide) (PNIPAM) is well known to exhibit reentrant behavior or cononsolvency in response to the composition of a mixed solvent consisting of water and a low‐chain alcohol. Since the solvent structure plays an important role in this phenomenon, the presence of structure‐breaking/structure‐making ions in solution is expected to have a dramatic effect on the cononsolvency of PNIPAM. The present work examines the way that the presence of different salts can modify the reentrant‐phase diagram displayed by a cationic PNIPAM microgel in the mixed ethanol/water solvent. The effects of four Hofmeister anions—SO42?, Cl?, NO3? and SCN?—with different abilities to modify the solvent structure are analyzed. The species with kosmotropic or structure‐making character show a clear competition with ethanol for the water molecules, intensifying the nonsolvency of the PNIPAM with the EtOH volume fraction (?e). However, striking results are found with the most chaotropic or structure‐breaking anion, SCN?. In contrast to what happens in water‐rich solutions, the presence of SCN? in alcohol‐rich solvents enhances the solubility of the polymer, which macroscopically results in the microgel swelling. Moreover, this ion displays great stabilizing properties when ?e> is 0.2. These results have been explained by considering how chaotropic or structure‐breaking ions interact with water and ethanol molecules.  相似文献   

9.
A novel electron‐deficient heteroacene 15H‐pyrazino[2″,3″:3′,4′]pyrrolo[1′,2′:1,2]imidazo[4,5‐b]phenazin‐15‐one ( 1 ) has been successfully synthesized and characterized. Compound 1 can selectively recognize CN? and F? over other 10 anions including BF4?, PF6?, Cl?, SO42?, NO3?, I?, H2PO4?, ClO4?, Ac?, and Br? in CHCl3/DMF mixed solvents with dual responses, including absorption signals and fluorescent “turn‐off” effects. CN? and F? can be distinguished by the completely quenched fluorescence (for CN?) and partially reduced fluorescence (for F?). Especially, compound 1 exhibits higher sensitivity to CN? than F? with the response concentration as low as 5.0 × 10?6 mol/L. Moreover, compound 1 shows very interesting solvatochromism effect, and the CHCl3 solution of compound 1 is sensitive to triethylamine, and its emission could change from green to red upon the addition of triethylamine, which is attributed to the n–π intermolecular charge‐transfer interaction.  相似文献   

10.
This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4D) for the separation and detection of inorganic anions in post‐blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C4D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 Vpp. The separation of Cl?, NO3?, NO2?, SO42?, ClO4? and ClO3? was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 104 and 1.7 × 105 plates/m. The found limits of detection ranged between 2.5 and 9.5 μmol/L. Last, real samples of post‐blast explosive residues were analyzed on the ME‐C4D devices obtaining successfully the determination of Cl?, NO3? and SO42?. The achieved concentration values varied between 12.8–72.5 mg/L for Cl?, 1.7–293.1 mg/L for NO3? and 1.3–201.3 mg/L for SO42?. The data obtained using ME‐C4D devices were in good agreement with the concentrations found by ion chromatography. The approach reported herein has provided short analysis time, instrumental simplicity, good analytical performance and low cost. Furthermore, the ME‐C4D devices emerge as a powerful and portable analytical platform for on‐site analysis demonstrating to be a promising tool for the crime scene investigation.  相似文献   

11.
A phenylenediamine‐capped conjugate of calix[4]arene ( Lamino ) was synthesized by reducing its precursor, Limino , with sodium borohydride in methanol. The Lamino sample binds to anions due to the more flexible and bent conformation of the capped aminophenolic binding core, compared to the precursor Limino . The Lamino sample showed selectivity towards H2PO4? by exhibiting a ratiometric increase in emission by about 11‐fold with a detection limit of (1.2±0.2) μm ((116±20) ppb) over 15 anions studied, including other phosphates, such as P2O74?, adenosine monophosphate (AMP2?), adenosine diphosphate (ADP2?), and adenosine triphosphate (ATP2?). The Lamino sample shows an increase in the absorbance at λ=315 nm in the presence of H2PO4?, CO32?, HCO3?, CH3CO2?, and F?. The 1H NMR spectroscopic titration of Lamino with H2PO4?, F?, and CH3CO2? showed major changes in the phenylene‐capped and salicyl moieties, and thereby, confirming the aminophenolic region as the binding core. However, the binding strength of these anions followed the trend H2PO4?>F??CH3CO2?>HSO4?. The heat changes observed by isothermal titration calorimetry support this trend. The Lamino sample showed reversible sensing towards H2PO4? and F? in the presence of Mg2+ and Ca2+, respectively. NOESY studies of Lamino , in comparison with its anionic complexes, revealed that major conformational changes occurred in the capping region to facilitate the binding of anion. ESI‐MS and the Job's method revealed 1:1 stoichiometry between Lamino and H2PO4? or F?. In the SEM micrographs of Lamino , the spherical particles are converted into spherical aggregates and further form large agglomerates and even branched sheets in the presence of anions, depending upon their binding strength.  相似文献   

12.
When the amide‐containing receptor 1 + is in a solution of dimethyl sulfoxide (DMSO) in the presence of basic anions (CH3COO?, F?, H2PO4?), it undergoes deprotonation of the ‐NH fragment to give the corresponding zwitterion, which can be isolated as a crystalline solid. In the presence of less basic anions (Cl?, Br?, NO3?), 1 + establishes true hydrogen‐bond interactions of decreasing intensity. The less acidic receptor 2 + undergoes neat proton transfer with only the more basic anions CH3COO? and F?, and establishes hydrogen‐bond interactions with H2PO4?. An empirical criterion for discerning neutralisation and hydrogen bonding, based on UV/Vis and 1H NMR spectra, is proposed.  相似文献   

13.
A series of C3i‐symmetric bicapped trigonal antiprismatic Cd8 cages [2X@Cd8L6(H2O)6] ? n Y ? solvents (X=Cl?, Y=NO3?, n=2: MOCC‐4 ; X=Br?, Y=NO3?, n=2: MOCC‐5 ; X=NO3?, Y=NO3?, n=2: MOCC‐6 ; X=NO3?, Y=BF4?, n=2: MOCC‐7 ; X=NO3?, Y=ClO4?, n=2: MOCC‐8 ; X=CO32?, n=0: MOCC‐9 ), doubly anion templated by different anions, were solvothermally synthesized by means of a flexible ligand. Interestingly, the CO32? template for MOCC‐9 was generated in situ by two‐step decomposition of DMF solvent. For other MOCCs, spherical or trigonal monovalent anions could also play the role of template in their formation. The template abilities of these anions in the formation of the cages were experimentally studied and are discussed for the first time. Anion exchange of MOCC‐8 was carried out and showed anion‐size selectivity. All of the cage‐like compounds emit strong luminescence at room temperature.  相似文献   

14.
Novel fluorescent chemosensor with good selectivity for F? anion was designed and synthesized. The sensor has a bearing on a single functionalized pillar[5]arene and Fe3+ metal complex (PN‐Fe), which showed prominent fluorescent response for F? anion over other common anions (Cl?, Br?, I?, AcO?, HSO4?, H2PO4?, ClO4?, CN? and SCN?). These results were evaluated by fluorescent method. The detection limit of PN‐Fe to F? was calculated to be 2.50×10?7 mol/L. Moreover, the sensor PN‐Fe3+ might serve as a recyclable component in sensing materials.  相似文献   

15.
Geometries have been optimized using molecular-orbital calculations (a) with a 4-31G Gaussian basis set for carbanions CH2X? where X = H, CH3, NH2, OH, F, C?CH, CH?CH2, CHO, COCH3, CN, and NO2; and (b) with an STO -3G basis set for methyl acetate and acetyl deprotonated methyl acetate. All the carbanions containing unsaturated substituents are planar, with a considerable shortening of the C? X bond. Carbanions containing saturated substituents are pyramidal with the out-of-plane angle α increasing with the electronegativity of the substituent. Double-zeta basis set calculations give proton affinities over the range 449 (for CH3CH2?) to 355 kcal/mol (for CH2NO2?), with all unsaturated anions having smaller affinities than saturated anions. The correlation of proton affinities with 1s binding energies, and with charges on both the carbon of the anion and on the acidic proton of the neutral molecule are examined.  相似文献   

16.
Synthesis and Structural Studies on Molecular Oxovanadium Phosphonates Solvothermal syntheses at 373 K in the system (MePPh3)[VO2Cl2]/ RPO3H2 (R = tBu; Ph)/Template (T= Cl?, HCl, OH?; Br?) /MeCN have lead to the already known compound [(VO)6(tBuPO3)8 ? Cl?] ( 1 ) [1] as well as to [(VO)6(tBuPO3)8 ? T](T: HCl ( 2 ) OH? 3 ), [(VO)6(PhPO3)8 ? Br?]×solv ( 4 ), (Ph3PMe)2[(VO)6(PhPO3)8 ? Cl?]3 ( 5 ) with an identical VPO‐core, and [(V3O5)(VO)4(tBuPO3)8 ? NO3?] ( 6 ) with seven metal centres. The renewed X‐ray structure analysis of 1 produced evidence, that the {V6P8O24}‐core shows some flexibility and belongs to the enantiomorphic point group O (≡ 432). With the structure data from the compounds 1 – 5 a geometric model for the flexible contraction of the {V6P8O24}‐core was developed. The calculation of the diameter of the host shell for different degrees of contraction shows that the {V6P8O24}‐core is always too small to incorporate a nitrate ion. This leads to the formation of [(V3O5)(VO)4(tBuPO3)8 ? NO3?] ( 6 ) which can be derived topologically from 1 . There is no structural similarity between 6 and the seven oxovanadium units containing anion of (Ph4P)2[(V4O7)(V3O5)(PhPO3)6 ? Cl?] [2]. The thermal degradation of 1 in air starts at 590 K with the oxidation of the organic groups followed by the formation of β‐(VO)(PO3)2. Possibly these results offer new ways to use oxovanadium phosphonates as precursors of oxovanadium phosphate catalysts.  相似文献   

17.
Three fluorescent turn‐on probes containing 3,6‐dichloro‐9H‐carbazole as carbazyl part have been designed and synthesized. Among studied anions F?, AcO?, H2PO , Cl?, Br? and I?, AcO? showed the strongest binding ability with all probes. The strong basic anions, such as AcO?, H2PO , and F?, induced a significant red‐shift in absorption and a concomitant increase in fluorescent emission of the probes caused by photoinduced electron transfer (PET). The determination limit of probe 3 (Scheme 1) toward AcO? is 3.0×10?7 M . 1H‐NMR Titration experiments shed light on the nature of the interaction between the probes and the anions. Theoretical investigation further illustrated the possible binding mode in these host? guest interactions and the roles of molecular frontier orbitals in molecular interplay.  相似文献   

18.
CF3H as a proton donor was paired with a variety of anions, and its properties were assessed by MP2/aug‐cc‐pVDZ calculations. The binding energy of monoanions halide, NO3?, formate, acetate, HSO4?, and H2PO4? lie in the 12–17 kcal mol?1 range, although F? is more strongly bound, by 26 kcal mol?1. Dianions SO42? and HPO42? are bound by 27 kcal mol?1, and trianion PO43? by 45 kcal mol?1. When two O atoms are available on the anion, the CH???O? H‐bond (HB) is usually bifurcated, although asymmetrically. The CH bond is elongated and its stretching frequency redshifted in these ionic HBs, but the shift is reduced in the bifurcated structures. Slightly more than half of the binding energy is attributed to Coulombic attraction, with smaller contributions from induction and dispersion. The amount of charge transfer from the anions to the σ*(CH) orbital correlates with many of the other indicators of bond strength, such as binding energy, CH bond stretch, CH redshift, downfield NMR spectroscopic chemical shift of the bridging proton, and density at bond critical points.  相似文献   

19.
A new ion selective electrode for salicylate based on N,N'-(aminoethyl)ethylenediamide bis(2-salicylideneimine) binuclear copper(Ⅱ) complex [Cu(Ⅱ)2-AEBS] as an ionophore was developed. The electrode has a linear range from 1.0 × 10^-1 to 5.0 ×10^-7 mol·L^- 1 with a near-Nemstian slope of ( - 55 ±1 ) mV/decade and a detection limit of 2.0 × 10-7 mol·L^-1 in phosphorate buffer solution of pH 5.0 at 25 ℃. It shows good selectivity for Sal^- and displays anti-Hofmeister selectivity sequence: Sal^-〉SCN^-〉 ClO4^- 〉I^-〉 NO2^- 〉Br^-〉 NO3^- 〉Cl^-〉 SO3^2- 〉 SO4^2- The proposed sensor based on binuclear copper(Ⅱ)complex has a fast response time of 5-10 s and can be used for at least 2 months without any major deviation. The response mechanism is discussed in view of the alternating current (AC) impedance technique and the UV-vis spectroscopy technique. The effect of the electrode membrane compositions and the experimental conditions were studied. The electrode has been successfully used for the determination of salicylate ion in drug pharmaceutical preparations.  相似文献   

20.
The synthesis of a novel [2]rotaxane host system containing a bis(triazolium)acridine‐based axle component is reported. 1H NMR anion‐binding titrations reveal that the rotaxane is able to recognise selectively the NO3? anion over a range of more basic oxoanions (AcO?, HCO3? and H2PO4?) in a competitive organic–aqueous solvent mixture.  相似文献   

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